CN106632794A - A method of preparing fluororubber through microemulsion polymerization - Google Patents
A method of preparing fluororubber through microemulsion polymerization Download PDFInfo
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- CN106632794A CN106632794A CN201611042819.XA CN201611042819A CN106632794A CN 106632794 A CN106632794 A CN 106632794A CN 201611042819 A CN201611042819 A CN 201611042819A CN 106632794 A CN106632794 A CN 106632794A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/22—Vinylidene fluoride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/28—Hexyfluoropropene
- C08F214/282—Hexyfluoropropene with fluorinated vinyl ethers
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Abstract
A method of preparing fluororubber through microemulsion polymerization is disclosed. The method includes (1) compounding fluoroether carboxylic acid or carboxylate polymer the molecular formula of which is CF3O(CF(CF3)CF2O)<a>(CF2CF2O)<b>COOX and a fluoroether oil polymer the molecular formula of which is CF3O(CF(CF3)CF2O)<c>(CF2CF2O)<d>CF3 according to a certain ratio to obtain an aqueous solution having a certain concentration; (2) subjecting one or a plurality of fluoroolefin monomers, a cure site monomer, a perfluoroether functional monomer and other olefin monomers according to a ratio to microemulsion polymerization in a polymerization kettle under actions of a fluorine-containing microemulsion surfactant, an initiator, and other auxiliary agents; and (3) subjecting the emulsion obtained through polymerization to coacervation, washing and drying for dehydration, and then preparing a fluororubber sheet resistant to low temperature through an open mill. Vulcanization, mechanical and low-temperature resistant properties of the fluororubber are effectively improved, the polymerization time is greatly shortened, and the production efficiency is increased.
Description
Technical field
The present invention relates to a kind of method for carrying out fluorubber preparation with micro-emulsion polymerization.
Background technology
During conventional emulsion polymerizations production fluorubber, perfluoro caprylic acid and its derivative because of its excellent surface-active and
Emulsifiability is widely used as a kind of emulsifying agent, due to the impact of " Teflon event ", the U.S. and European Union made laws in
Import is completely forbidden after 2015, the product containing perfluorooctanoic acid salt is used, therefore the fluorubber developed without perfluorooctanoic acid salt is clear
Clean production technology tool is of great significance.At present foreign countries' fewer companies have developed the substitute of perfluorooctanoic acid salt for fluorine
The perfluoro butyl sulfonic acid of rubber production, such as 3M companies（C4）, E.I.Du Pont Company the C6 base products containing hydrocarbon segment and day
The C6 products of this big King Company, and China's application study in this regard still belongs to blank.Therefore, how to find can in performance
It is a urgent and difficult task of the pendulum in face of us with the surfactant for replacing perfluoro caprylic acid.
The content of the invention
The invention provides a kind of method for carrying out fluorubber preparation with micro-emulsion polymerization, it not only can be effectively improved
The sulfuration of fluorubber, machinery and resistance to low temperature, and can significantly shorten polymerization time, improve production efficiency.
Present invention employs technical scheme below：A kind of method for carrying out fluorubber preparation with micro-emulsion polymerization, its feature
Comprise the following steps：
Step one, with molecular formula as CF3O(CF(CF3)CF2O)a(CF2CF2O)bThe fluorine ether carboxylic acid of COOX or carboxylate polymer and
Molecular formula is CF3O(CF(CF3)CF2O)c(CF2CF2O)dCF3Fluorine ether oil polymer compound prepared finite concentration by a certain percentage
The aqueous solution, as the surfactant of micro-emulsion polymerization；
Step 2, in the presence of the auxiliary agents such as fluorine-containing microemulsion surfactant, initiator, one or more fluorinated olefin monomers,
Cure site monomer, perfluoroether functional monomer and other olefinic monomers carry out microemulsion in polymeric kettle and gather by certain proportioning
Close；
Step 3, then polymerization gained latex Jing is condensed, washing makes low temperature resistant fluorubber glue after drying and dehydrating by mill
Piece.
X, Y described in step one is respectively H, NH4 or alkali metal ion, a be 3～9, b be 0～6, c be 10～
18, d is 0～8, and described fluorine ether carboxylic acid or the molecular weight of carboxylate is 500～1500, and acid number is 70～120；Fluorine ether oil
Molecular weight is 1500～3000, and described fluorine ether carboxylic acid or the quality proportioning of carboxylate and fluorine ether oil is 60：40～80：20, institute
The concentration of aqueous solution of the preparation micro-emulsion polymerization surfactant stated is 35%～65%.
Initiator in step 2 be persulfate, Persulphate-Bisulphite, di-isopropyl peroxydicarbonate,
TBHP, benzoyl peroxide or perfluor acyl peroxide.
A kind of fluorinated olefin monomers are tetrafluoroethene, vinylidene, hexafluoropropene or CTFE in step 2.
Various fluorinated olefin monomers are in tetrafluoroethene, vinylidene, hexafluoropropene or CTFE in step 2
Any two kinds of combinations or two or more combinations.
Cure site monomer is brominated monomer or monomer containing iodine in step 2.
Brominated monomer is the fluoro- 1- butylene of the bromo- 3,3,4,4- tetra- of 4-, bromo trifluoro-ethylene, the bromo- 1,1- difluoroethylenes of 2-, 3-
Bromo- 2,2,3,3- tetrafluoro-1-propenes or bromo- 1,1, the 2- tri- fluoro- 1- butylene of 4-, monomer containing iodine is Isosorbide-5-Nitrae-diiodo perfluo butane or 1,
The difluoro hexane of bis- iodos of 6- ten.
Perfluoroether functional monomer is perfluorovinyl sulfide alkyl oxide monomer CF in step 22=CF-O-Rf, Rf are CnF2n+
1, n=1～5 or hexafluoropropylene-based alkyl oxide monomer CF2=CFCF2- O-Rf, Rf are CnF2n+1, n=1～5.
Perfluorovinyl sulfide alkyl oxide monomer is perfluorovinyl sulfide methyl ether CF2=CF-O-CF3, perfluoroethylene benzyl ethyl ether CF2
=CF-O-C2F5Or perfluorovinyl sulfide propyl ether CF2=CF-O-C3F7；Hexafluoropropylene-based alkyl oxide monomer is perfluoropropene ylmethyl
Ether CF2=CFCF2-O-CF3, perfluoropropene benzyl ethyl ether CF2=CFCF2-O-C2F5Or hexafluoropropylene-based propyl ether CF2=CFCF2-O-
C3F7。
Other olefinic monomers are ethene or propylene in step 2, and the addition of described polymeric component presses 100 with distilled water
Listed as parts by weight, remaining auxiliary agent is respectively：Fluorine-containing microemulsion surfactant 1～8, initiator 0.05～0.2.
The invention has the advantages that：After employing above technical scheme, invention discloses a kind of use
The environment-friendly type micro emulsion surfactant of various fluorine ether polymer compoundings is used for the preparation of fluorubber, it is to avoid using to environment, biology
Harmful perfluoro caprylic acid and its derivative；Particularly preparing peroxide cure fluorubber, perfluoroether fluorubber and low temperature fluorine
During rubber, the generation of gel is avoided that, is effectively improved sulfuration, machinery and the resistance to low temperature of fluorubber；And with perfluor
Caprylate is made to compare during emulsifying agent, can significantly shorten polymerization time, improve production efficiency.
Specific embodiment
A kind of method for carrying out fluorubber preparation with micro-emulsion polymerization of the present invention, its feature is comprised the following steps：
Step one, with molecular formula as CF3O(CF(CF3)CF2O)a(CF2CF2O)bThe fluorine ether carboxylic acid of COOX or carboxylate polymer and
Molecular formula is CF3O(CF(CF3)CF2O)c(CF2CF2O)dCF3Fluorine ether oil polymer compound prepared finite concentration by a certain percentage
The aqueous solution, as the surfactant of micro-emulsion polymerization, X, the Y described in step one is respectively H, NH4 or alkali metal
Ion, it is that 10～18, d is 0～8 for 0～6, c that a is 3～9, b, and described fluorine ether carboxylic acid or the molecular weight of carboxylate is
500～1500, acid number is 70～120；The molecular weight of fluorine ether oil is 1500～3000, described fluorine ether carboxylic acid or carboxylate and fluorine
The quality proportioning of ether oil is 60：40～80：20, the concentration of aqueous solution of described preparation micro-emulsion polymerization surfactant is 35%
～65%.；
Step 2, in the presence of the auxiliary agents such as fluorine-containing microemulsion surfactant, initiator, one or more fluorinated olefin monomers,
Cure site monomer, perfluoroether functional monomer and other olefinic monomers carry out microemulsion in polymeric kettle and gather by certain proportioning
Close, initiator be persulfate, Persulphate-Bisulphite, di-isopropyl peroxydicarbonate, TBHP,
A kind of benzoyl peroxide or perfluor acyl peroxide, fluorinated olefin monomers are tetrafluoroethene, vinylidene, hexafluoropropene or three
Fluorine vinyl chloride, various fluorinated olefin monomers are any two kinds in tetrafluoroethene, vinylidene, hexafluoropropene or CTFE
Combination or two or more combinations, cure site monomer is brominated monomer or monomer containing iodine, and brominated monomer is 4- bromo- 3,3,4,4- tetra-
The bromo- 1,1- difluoroethylenes of fluoro- 1- butylene, bromo trifluoro-ethylene, 2-, the bromo- 2,2,3,3- tetrafluoro-1-propenes of 3- or 4- bromo- 1,1,
The fluoro- 1- butylene of 2- tri-, monomer containing iodine is Isosorbide-5-Nitrae-diiodo perfluo butane or the difluoro hexane of bis- iodo of 1,6- ten, perfluoroether in step 2
Functional monomer is perfluorovinyl sulfide alkyl oxide monomer CF2=CF-O-Rf, Rf are CnF2n+1, n=1～5 or hexafluoropropylene-based alkane
Base ether monomer CF2=CFCF2- O-Rf, Rf are CnF2n+1, and n=1～5, perfluorovinyl sulfide alkyl oxide monomer is perfluoroethylene ylmethyl
Ether CF2=CF-O-CF3, perfluoroethylene benzyl ethyl ether CF2=CF-O-C2F5Or perfluorovinyl sulfide propyl ether CF2=CF-O-C3F7；Perfluor
Acrylic alkyl oxide monomer is hexafluoropropylene-based methyl ether CF2=CFCF2-O-CF3, perfluoropropene benzyl ethyl ether CF2=CFCF2-O-
C2F5Or hexafluoropropylene-based propyl ether CF2=CFCF2-O-C3F7, other olefinic monomers are ethene or propylene, described polymeric component
Addition 100 listed as parts by weight are pressed with distilled water, remaining auxiliary agent is respectively：Fluorine-containing microemulsion surfactant 1～8, initiator
0.05～0.2.；
Step 3, then polymerization gained latex Jing is condensed, washing makes low temperature resistant fluorubber glue after drying and dehydrating by mill
Piece.
To be best understood from the present invention, the present invention is described in further detail with reference to embodiment, but it is of the invention
Claimed scope is not limited to the scope that embodiment is represented.
Embodiment 1：
The present embodiment carries out the preparation of micro emulsion surfactant with fluorine ether carboxylate and fluorine ether oil as raw material：
The deionized water of 4kg is added in the container of 10L, 1.8kg structural formulas are CF3O(CF(CF3)CF2O)3(CF2CF2O)5COONH4Fluorine ether carboxylate, 1.0kg structural formulas be CF3O(CF(CF3)CF2O)12(CF2CF2O)2CF3Fluorine ether oil, in normal temperature
Stir under normal pressure, just obtain the aqueous solution of the micro emulsion surfactant that concentration is 41.2%.
Embodiment 2：
The deionized water of 4kg is added in the container of 10L, 3.8kg structural formulas are CF3O(CF(CF3)CF2O)8COONH4Fluorine ether
Carboxylate, 1.6kg structural formulas are CF3O(CF(CF3)CF2O)10(CF2CF2O)4CF3Fluorine ether oil, stir at normal temperatures and pressures equal
It is even, just obtain the aqueous solution of the micro emulsion surfactant that concentration is 57.4%.
Embodiment 3：
By taking 100L polymeric kettles as an example, 60kg deionized waters, the micro emulsion surface that 1.2kg embodiments one are prepared are added in a kettle.
Activating agent；Jing nitrogen displacements and process is vacuumized, in kettle after oxygen content≤20ppm；Mass ratio is added to be 60 into kettle：40 it is inclined
PVF, hexafluoropropene mix monomer, are 2.1 Mpa to kettle pressure；Stir, be warming up to 92 DEG C, add the persulfuric acid that concentration is 5%
Potassium initiator 1.2Kg starts reaction, monomer mixture is continuously added in course of reaction pressure is maintained at into 2.1Mpa；When reaction one
Stop reaction after quantitative, unreacted mix monomer is reclaimed after cooling；Polymerization gained latex Jing cohesions, washing is dried
Binary fluorine rubber rubber is obtained by mill after dehydration.
Be shown in Table 1, fluorubber obtained in embodiment 3 with perfluoro caprylic acid as emulsifying agent be obtained fluorubber contrasted, remaining
Operation is same as Example 3.
The fluorubber performance comparison of the different emulsifiers of table 1 production
Embodiment 4：
By taking 100L polymeric kettles as an example, 60kg deionized waters, the micro emulsion surface that 1.5kg embodiments one are prepared are added in a kettle.
Activating agent and 60g molecular weight regulator diethyl malonates；Jing nitrogen displacements and process is vacuumized, oxygen content≤20ppm in kettle
Afterwards；Mass ratio is added to be 27 into kettle：41：32 tetrafluoroethene, vinylidene, hexafluoropropene mix monomer, is 2.4 to kettle pressure
Mpa；Stir, be warming up to 88 DEG C, add ammonium persulfate initiator 1.4Kg that concentration is 5% to start reaction, it is continuous in course of reaction
Add monomer mixture and pressure is maintained at into 2.4Mpa；Stop reaction after reacting a certain amount of, to unreacted mixing after cooling
Monomer is reclaimed；Polymerization gained latex Jing cohesions, washing obtains ternary fluororubber rubber after drying and dehydrating by mill.
Be shown in Table 2, fluorubber obtained in embodiment 4 with perfluoro caprylic acid as emulsifying agent be obtained fluorubber contrasted, remaining
Operation is same as Example 4.
The fluorubber performance comparison of the different emulsifiers of table 2 production
Embodiment 5：
By taking 100L polymeric kettles as an example, 60kg deionized waters, the micro emulsion surface that 3kg embodiments two are prepared is added to live in a kettle.
Property agent and the fluoro- difluoro hexane 70g of bis- iodos of 1- butylene 120g, 1,6- ten of the bromo- 3,3,4,4- tetra- of cure site monomer 4-；Jing nitrogen is put
Process is changed and vacuumizes, in kettle after oxygen content≤20ppm；Mass ratio is added to be 25 into kettle：38：37 tetrafluoroethene, inclined fluorine
Ethene, hexafluoropropene mix monomer, are 1.8 Mpa to kettle pressure；Stir, be warming up to 80 DEG C, add the ammonium persulfate that concentration is 5%
Initiator 1.4Kg starts reaction, monomer mixture is continuously added in course of reaction pressure is maintained at into 1.8Mpa；It is certain when reacting
Stop reaction after amount, unreacted mix monomer is reclaimed after cooling；Polymerization gained latex Jing cohesions, washing is dried de-
Peroxide cure crude fluororubber is obtained by mill after water.
Be shown in Table 3, fluorubber obtained in embodiment 5 with perfluoro caprylic acid as emulsifying agent be obtained fluorubber contrasted, remaining
Operation is same as Example 5.
The fluorubber performance comparison of the different emulsifiers of table 3 production
Embodiment 6：
By taking 100L polymeric kettles as an example, 60kg deionized waters, the micro emulsion surface that 3.2kg embodiments two are prepared are added in a kettle.
Activating agent, 1,4- diiodo perfluo butane 100g；Jing nitrogen displacements and process is vacuumized, in kettle after oxygen content≤20ppm；Into kettle
Mass ratio is added to be 35：40：25 vinylidene, hexafluoropropene, perfluorovinyl sulfide propyl ether mix monomer, is 2.0 to kettle pressure
Mpa；Stir, be warming up to 83 DEG C, add potassium peroxydisulfate initiator 1.6Kg that concentration is 5% to start reaction, it is continuous in course of reaction
Add monomer mixture and pressure is maintained at into 2.0Mpa；Stop reaction after reacting a certain amount of, to unreacted mixing after cooling
Monomer is reclaimed；Polymerization gained latex Jing cohesions, washing obtains the life of perfluoroether low temperature fluorubber after drying and dehydrating by mill
Glue.
Be shown in Table 4, fluorubber obtained in embodiment 6 with perfluoro caprylic acid as emulsifying agent be obtained fluorubber contrasted, remaining
Operation is same as Example 6.
The fluorubber performance comparison of the different emulsifiers of table 4 production
Claims (10)
1. a kind of method for carrying out fluorubber preparation with micro-emulsion polymerization, its feature is comprised the following steps：
Step one, with molecular formula as CF3O(CF(CF3)CF2O)a(CF2CF2O)bThe fluorine ether carboxylic acid of COOX or carboxylate polymer and
Molecular formula is CF3O(CF(CF3)CF2O)c(CF2CF2O)dCF3Fluorine ether oil polymer compound prepared finite concentration by a certain percentage
The aqueous solution, as the surfactant of micro-emulsion polymerization；
Step 2, in the presence of the auxiliary agents such as fluorine-containing microemulsion surfactant, initiator, one or more fluorinated olefin monomers,
Cure site monomer, perfluoroether functional monomer and other olefinic monomers carry out microemulsion in polymeric kettle and gather by certain proportioning
Close；
Step 3, then polymerization gained latex Jing is condensed, washing makes low temperature resistant fluorubber glue after drying and dehydrating by mill
Piece.
2. the method for carrying out fluorubber preparation with micro-emulsion polymerization according to claim 1, is characterized in that institute in step one
X, the Y for stating is respectively H, NH4 or alkali metal ion, and it is 0～8 for 10～18, d for 0～6, c that a is 3～9, b, described
The molecular weight of fluorine ether carboxylic acid or carboxylate is 500～1500, and acid number is 70～120；The molecular weight of fluorine ether oil is 1500～3000,
Described fluorine ether carboxylic acid or the quality proportioning of carboxylate and fluorine ether oil is 60：40～80：20, described preparation micro-emulsion polymerization table
The concentration of aqueous solution of face activating agent is 35%～65%.
3. the method for carrying out fluorubber preparation with micro-emulsion polymerization according to claim 1, in it is characterized in that step 2
Initiator is persulfate, Persulphate-Bisulphite, di-isopropyl peroxydicarbonate, TBHP, peroxide
Change benzoyl or perfluor acyl peroxide.
4. the method for carrying out fluorubber preparation with micro-emulsion polymerization according to claim 1, is characterized in that one in step 2
It is tetrafluoroethene, vinylidene, hexafluoropropene or CTFE to plant fluorinated olefin monomers.
5. the method for carrying out fluorubber preparation with micro-emulsion polymerization according to claim 1, is characterized in that many in step 2
It is that any two kinds in tetrafluoroethene, vinylidene, hexafluoropropene or CTFE are combined or two kinds to plant fluorinated olefin monomers
Combination above.
6. the method for carrying out fluorubber preparation with micro-emulsion polymerization according to claim 1, is characterized in that sulphur in step 2
It is brominated monomer or monomer containing iodine to change point monomer.
7. the method for carrying out fluorubber preparation with micro-emulsion polymerization according to claim 6, is characterized in that brominated monomer is
The fluoro- 1- butylene of the bromo- 3,3,4,4- tetra- of 4-, bromo trifluoro-ethylene, the bromo- 1,1- difluoroethylenes of 2-, the 3- fluoro- 1- of bromo- 2,2,3,3- tetra-
Propylene or bromo- 1,1, the 2- tri- fluoro- 1- butylene of 4-, monomer containing iodine be Isosorbide-5-Nitrae-diiodo perfluo butane or the difluoro of bis- iodo of 1,6- ten oneself
Alkane.
8. the method for carrying out fluorubber preparation with micro-emulsion polymerization according to claim 1, is characterized in that complete in step 2
Fluorine ether functional monomer is perfluorovinyl sulfide alkyl oxide monomer CF2=CF-O-Rf, Rf are CnF2n+1, n=1～5 or perfluoropropene
Base alkyl oxide monomer CF2=CFCF2- O-Rf, Rf are CnF2n+1, n=1～5.
9. the method for carrying out fluorubber preparation with micro-emulsion polymerization according to claim 8, is characterized in that perfluorovinyl sulfide
Alkyl oxide monomer is perfluorovinyl sulfide methyl ether CF2=CF-O-CF3, perfluoroethylene benzyl ethyl ether CF2=CF-O-C2F5Or perfluor second
Thiazolinyl propyl ether CF2=CF-O-C3F7；Hexafluoropropylene-based alkyl oxide monomer is hexafluoropropylene-based methyl ether CF2=CFCF2-O-CF3,
Perfluoropropene benzyl ethyl ether CF2=CFCF2-O-C2F5Or hexafluoropropylene-based propyl ether CF2=CFCF2-O-C3F7。
10. the method for carrying out fluorubber preparation with micro-emulsion polymerization according to claim 1, in it is characterized in that step 2
Other olefinic monomers are ethene or propylene, and the addition of described polymeric component presses 100 listed as parts by weight with distilled water, remaining
Auxiliary agent is respectively：Fluorine-containing microemulsion surfactant 1～8, initiator 0.05～0.2.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111363076A (en) * | 2020-04-24 | 2020-07-03 | 四川道弘科技有限公司 | Ternary peroxide fluororubber and preparation method thereof, and intelligent wearing material and preparation method thereof |
| CN112542588A (en) * | 2019-09-20 | 2021-03-23 | 浙江蓝天环保高科技股份有限公司 | Vinylidene fluoride copolymer, and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101302262A (en) * | 2008-07-04 | 2008-11-12 | 山东东岳神舟新材料有限公司 | Preparation of ethylene-tetrafluoroethylene copolymer |
| JP2009161532A (en) * | 2008-01-03 | 2009-07-23 | Daikin Ind Ltd | Fluoroether carboxylic acid, surfactant, production method of fluorine-containing polymer using the same and aqueous dispersion |
| CN102432725A (en) * | 2011-08-29 | 2012-05-02 | 费植煌 | Preparation method and application of fluorine-containing resin |
| CN104530292A (en) * | 2014-12-19 | 2015-04-22 | 中昊晨光化工研究院有限公司 | Low-temperature-resistant perfluoroether rubber and synthesis method thereof |
-
2016
- 2016-11-24 CN CN201611042819.XA patent/CN106632794A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009161532A (en) * | 2008-01-03 | 2009-07-23 | Daikin Ind Ltd | Fluoroether carboxylic acid, surfactant, production method of fluorine-containing polymer using the same and aqueous dispersion |
| CN101302262A (en) * | 2008-07-04 | 2008-11-12 | 山东东岳神舟新材料有限公司 | Preparation of ethylene-tetrafluoroethylene copolymer |
| CN102432725A (en) * | 2011-08-29 | 2012-05-02 | 费植煌 | Preparation method and application of fluorine-containing resin |
| CN104530292A (en) * | 2014-12-19 | 2015-04-22 | 中昊晨光化工研究院有限公司 | Low-temperature-resistant perfluoroether rubber and synthesis method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112542588A (en) * | 2019-09-20 | 2021-03-23 | 浙江蓝天环保高科技股份有限公司 | Vinylidene fluoride copolymer, and preparation method and application thereof |
| CN111363076A (en) * | 2020-04-24 | 2020-07-03 | 四川道弘科技有限公司 | Ternary peroxide fluororubber and preparation method thereof, and intelligent wearing material and preparation method thereof |
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